New dyeing preparation and its conversion to dyestuffs



Patented Aug. 1, 1933 UNITED STATES PATENT OFFICE NEW DYEING PREPARATION AND ITS CONVERSION TO DYESTUFFS I Arthur Zitscher, Wilhelm Seidenfaden, and Karl Jellinek, Offenbach-on-the-Main,

Germany,

assignors to- General Aniline, Works, Inc., New York, N. Y., a Corporation of Delaware No Drawing; Application September 3, 1931, Serial No. 561,088, and in Germany September 20 Claims.

Our present invention relates to new dyein preparations-and their: conversion. to dyestuffs.

These dyeing preparatiOnscOntain a diazosulfonate of the diarylamine series correspond- 6 ing to the probable general formula:

wherein X means a naphthalene nucleus or a radical of the benzene series which may contain in the para-position to .the NH-group a further -N=NSOaalkali-metal group, and R means a radical of the benzene series, and a combining component containing a hydroxy ora O-alkali-metal group whereof the adjacent position is capable of attaching an 'arylazogroup.

As substituents presentin the benzene nuclei of the diazo-sulfonates" may be p fically named: 'alkyl, alkoxy, aryloxy, alkylmerca-pto, aroylamino, halogen, nitro, arylsulfonyl, arylaminocarbonyl. 1

2 The diazo-sulfonates we use. 1

methylene group capable of being combined with diazocompounds, as, for instance pyrazolones and derivatives of p-ketonaldehyde, for instance, acetoacetyl-amino-aryls and di-(aceto-acetylamino) -aryls '(see U. S. Patent Nos. 1,594,864, 1,594,866, 1,594,867, 1,580,709, 1,634,090); dihydroxy-quinolines (see U. S. applications Serial Nos. 352,317, 352,318, 352,319: British Patent No. 332,940) (2ehydroxy-carbazole-3-carbonyl) -amino-aryls, (2-hydroxy-benzocarbazole-3-carbon yl) amino-aryls,. (2-hydroxy-anthracene-ii-carbonyl) --amino-aryls.

in an alkaline medium to fibers, by steaming only, insoluble'azodyestufls on the fibers.

Such applying to the fibers consists in dyeing present invention are described and clairne 1 in the 00,-

These dyeing preparations yield, when applied according to the one-bath-method or in printing. The -"dyebath or the printing paste or also the powde'rous dyeing, preparations themselves are advantageously mixed with dyeing expedients having wetting, emulsifying or dissolving properties, or also with the additional agents customary in using nitrosamine-printing-colors,

, as, for instance chromate. Furthermore sulfur is advantageously added tothe printing paste. Therebythe quickness and the evennessot the dyestu'ff formation is favorably influenced.

In order to further illustrate j our invention the following examplesyare given, the parts being by weight and all temperatures in centigrade degrees. But we wish itto be understood that we are not limited to the particular. conditions or specific products mentioned therein.

Example I A printing, paste which contains:

63 parts of the sodium salt of diphenylamine- 4.4'-bisdiazo-sulfonic acid 25 parts of (2-hydroxy-naphthalenel-3-carbonyl-amino) benzene I 30 parts of caustic soda lye of 34 B.

20 parts of thiodiglycol 362 parts of water 500 parts of starch tragacanth-thickening is printed on textile materials. The goods thus printed are driecl, steamed for"? minutes in the Mather-Flatt, rinsed hot and shortly soaped.

In this manner abeautiful bluish black print is obtained.

Example 2 By using a printing paste which contains 20 parts 1-(2- hydroxy-carbazole 3 carbonyl-amino) -2-methyl-benz ene, 50 parts ofdiphenylamine-4.4-bis-diazosulfonateand the other ingredients of the paste used in'Example 1 and by working otherwise as described above, a pucebrown print is obtained.

4.4 -di- (aceto-acetylamino) -3.3' -dimethyl diphenyl yields by an analogous process a brown orange print.

Example 3 I A printing paste which contains: 20 parts of thesodium salt of 4'-met-hoxy-diphenyl-amine-4-diazo-su1fonicacid 15 parts of (2-hydroxy-naphthalene-3-carbonyl-amino) -benzene 20 parts of caustic soda lye of 34 B.

15 parts of thiodiglycol 430 parts of water I 500 parts of starch'tragacanth-thickening is printed on the materials. Then the goods are dried, steamed for 7 minutes in the Mather-Flatt, rinsed-hot, soaped and rinsed again.

In this manner a clear navy-blue print is obtained.

Diphenyl-amine-4-diazo-sulfonate yields when used in an analogous manner a more reddish navyblue print.

Example 4 A printing paste which contains 22 parts of the sodium salt of diphenyl-amine- 4.4-bis-diazo-sulfonic acid j 25 parts of 1-(2-hydroxy-naphthalene-3-carbonyl-amine) -2-methoxy-benzene 30 parts of caustic soda lye of 34 B.

8 parts of finely powdered suliur 20 parts of thiodiglycol 395 parts of water 500 parts of starch-tragacanth-thickening is'printed, the goods are steamed for 5 minutes,

'r'insecl hot and soaped. In this manner a full black print is obtained.

Example 5 g a A printing paste which contains:

201 parts of the sodium salt of 4'-methoxy-di phenyl aminei-diazo-sulionic-acid 15 parts of (2-hydroxy-naphthalene-3-carbonyl-amino)-benzene 20 parts of caustic soda lye of 34 B.

. 4 parts of finely powdered sulfur I 20 parts. of alcohol 15 parts of Turkey-red-oil 15 parts of sodium chromate solution 1:4 391 parts of water 500 parts of starch-tragacanth-thickening is printed. The goods are dried, steamed for 5- minutes in the Mather-Flatt and finished as described above.

. In this manner a dark navy-blue print is obtamed: by using a paste of lower concentration beautiful light blue shades are obtained.

Example 6 Example 7 A printing paste which contains: 16 parts of the sodium salt of 3-methoxy-diphenyl-amine-4-diazo-sulfonic-acid 15 parts of 1-(2-hydroxy-naphthalene-3-carbonyl-amino) -3-nitro-benzene 30 parts of alcohol 5 parts of caustic soda lye-of 34 B. 5 parts of thiodiglykol 454 parts of water 450 parts of starch-tragacanth-thickening 15 parts of neutral chromate solution 1:4 is printed. The goods are dried, steamed for 7 26.3 parts 30.0 parts of the disodium minutes in the Mather-Flatt and finished as described above.

In this manner a greenish blue print is obtained.

Example 8 A mixture of 32.0 parts of the sodium salt of 4-methoxy-diphenyl-amine-4-diazo-sulfonic-acid of (2hydroxy-naphthalene-3-carbonyl-amino) -benzene 6.0 parts of finely ground sulfur 8.0 parts powdered sodium hydroxide is ground together. The mixture is made up to a printing paste. This paste is printed on the materials, which are then steamed and washed.

In this manner a clear navy blue print is obtained.

Example 9 A mixture of: 10.6 parts ofthe sodium salt of 3-methoxy-diphenyl-amine-4-diazo sulfonic-acid 10.0 parts of 1-(-2-hydroxy-naphthalene-3-carbonyl-amino) -3-nitro -benzene 3.0 parts of sodium hydroxide is ground together. The mixture is made up to a printing paste. This'paste is printed on the materials, which are then steamed and washed.

In this manner a greenish blue print is obtained.

I Example 10 A mixture of:

salt of diphenylamine- 4.4'-bis-diazo-sulionic acid 28.6 parts of the di-sodium salt of 1-(2-hydroxynaphthalene-3 -carbonyl-amino) 3 nitrobenzene i 8.0 parts of flowers of sulfur is ground together. The mixture is made up to a printing paste, advantageously with the addition of caustic soda lye. This paste is printed on the materials, which are then steamed and washed.

In this manner a black print is. obtained.

In the following table we have inserted the shades of a series of further dyeings or prints, produced in an analogous manner:

Salt of the diazosulionic (Zhydrox -naphthalene-3- acid of carbonyi compound of shade 4amino-diphenyiamine... Z-amino-l-ethoxy-benzene. Dark-blue Do 5-chloro-2-amino-1-rneth- Navy-blue oxy-benzene Do 2-amino-1-phcnoxy-ben- Blue zene 4-amino-2-methyl-dil-amino-2.5din1ethoxy-' Reddish phenylamine benzene gavylue 4-81111110 4 2: methoxy di Z-amino-l-ethyl-benzene. D ark-viophenylamine let Do. 2-amino-3-methoxy-naph- B l a c k is h 'thalene blue 4-11 m i n o-2'-e t h o x 37-61 i- Z-amino-naphthalene Dark-blue phenylamine o 2-amino-4-chloro-1-ethyl- Dark-blue benzene 4-2; m 1 n o-2-p h e n ox y-d llethoxy-l-amino benzenea R e d dis h phenylamlne navya blue 4- ainmo 2' chloro diphe 3-nitro-l-amino-benzene Dark-blue nylamine Do l-amino-4-ethyl-benzene. R e d d is h v navyblue 4-ammo-3' -methyl-d1- fi-chloro-Z-amino-l- Reddish phenylamine methoxy-benzene navy 2 b no 4-amino-3'- !nethoxy-di- Z-amino-l-methyI-benzene. Reddish phenylamlne darkblue 4- am1no -3'- chloro diplie 3-amino-i-methyl-benzene Navy-blue nylamine v 4-amino-4 -methyl-di- 4-aminol-methy1-benzene Reddish phenylamine darkblue Salt oi the diazosullonic acid of (z-hydroxy-naphthalenecarbonyl) compound of shade -amin0-4- etbox di he- 1 -(6 bromo 2 hydroxy- Greenish 4 nylarnine y p naphthalene -3- carbonblue ylamino) naphthalene Do lA-di- (2-hydroxy-neph- Navy blue thalene j- 3 earbonylamino) 2 methyl 5 memory-benzene Do 4.4" di -(2 hydroxy-naph- Greenish thalene -3 carbonylnmblue ino)-benzo-phenone 4 amino 3 Iuethoxy-dil-(2 hydroxy anthracene- Bluish phenylamine 3 carbonyl amino)-2- green methyl-benzene 4.4'-diamino diphenylani 2-hydroxynaphthalene..'. Corinth ine Do l-(2 hydro: naphtha Black lene 3 4 car nylamino)- Z-methyl-benzene Do 2-(2 hydroxy naphtha- Black a lone 3 carbonylamino)- i naphthalene 4.4'- diamino- 2 chlolo (2 hydroxy naphtha Black 3.3- dimethyldiphenyl leno 3 -'ca.rbonylamm0)- amine benzene which dyestufis are insoluble in water, and alkalies, it is to be understood that the aromatic nuclei of the general formula: appearing in the appended claimscontain no substituents as are known to render organic compounds soluble in water or alkalies and to tend todepreciate the fastness of the dyestufls to alkalies. Substituents I 0: this kind are the sulfonic acid, the carboxylic H acid and the hydroxy group,

We claim: I v 1. Asnew' compositions of matter the dyeing preparations comprising a diazo-sulfonate of the diaryl-amine series corresponding to the probable general formula:

X--NH--R--N=NSO alkaliemetal wherein X means a naphthalene nucleus or a radical of the benzene series which may contain in the para-position tothe NH-group a further 4 --N=NS0a-alkali-metal group and R means a radical of the benzene series and 1a combining component containing a hydroxy or a O-alkalidiarylamine series corresponding to the probable general formula;

X-NH-RN=N-SOa-alkali-metal wherein X means a naphthalene nucleus or a radical of the benzene series which may contain in the para-position to the NH-group a further --N=NSO5-a1kali-metal group and R means a radical of the benzene series and an azo coupling component which contains a hydroxy or a O- alkali-metal, group, a free ortho-position relative to thesaidgroup capable of attaching an arylazo group and which may contain as substituents aroylamino, aroyl, arylaminocarbonyl, which dyeing preparations yield in the presence of caustic alkali by steaming azodyestuifs insoluble in water and alkali.

3. As new compositions of matter the dyeing preparations comprising a diazo-sulfonate of the diphenylamine series corresponding to the probable general formula wherein the benzene nuclei may contain alkyl,

. alkoxy, aryloxy, halogen or nitro and Y means hydrogen or one of the aforesaid substituents or a second-N:N--SOa-alkali-metal group and a combining component containing a hydroxy or a O-alkali-metal group whereof the adjacent position is capable of attaching an arylazo group,

which dyeing preparations yield in the presence YQNHON=NSOa-alkali-metal wherein the benzene nuclei may contain alkyl, alkoxy, aryloxy, halogen or nitro and Y means hydrogen or one of the aforesaid substituents or a second-N:N--SOa--alkali-metal group and an azo coupling component which contains a hydroxy or a Q-alkali-metal group, a free orthoposition relative to the said group capable of attaching an arylazo group and which may contain as substituents aroylamino, aroyl, arylaminocarbonyl, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestuffs insoluble in water and alkali.

5. As new compositions of matter the dyeing preparations comprisinga diazo-sulfonate of the diaryl-amine series corresponding to the probable general formula:

XNHR--N=N--SOa-alkali-meta1 wherein X means a naphthalene nucleus or a radical of the benzene serieswhich may contain in the para-position to the NH-group a further -N=N-SOa--a1ka1i-metal group and R means a radical of the benzene series, and a (2-hydroxynaphthalene-Ii-carbonyl) -amino-aryl of the formula:

wherein Z means a radical of the benzene or naphthalene series, which dyeing preparations yield in the presence of caustic alkali by steam ing azo-dyestuffs insoluble in water and alkali.

6. As new compositions of matter the dyeing preparations comprising a diazo-sulfonate of the diphenylamine series corresponding to the probable general formula:

wherein the benzene nuclei may contain alkyl, alkoxy, aryloxy, halogen or nitro and Y means hydrogen or one of the aforesaid substituents or a second-N=NSO3-alkali-metal group, and a (2 hydroxy-naphtha1ene-3-carbonyl) aminoaryl of the formula:

wherein Z means a radical of the benzene or naphthalene series, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestuffs insoluble in water and alkali.

7. As new compositions of matter the dyeing;

preparations comprising a diazo-sulfonate of the diphenylamine series corresponding to the probable general formula:

wherein the benzene nuclei may contain alkyl, alkoxy, aryloxy, halogen or nitro, and a (2-hydroxy-naphthalene-3 -carbonyl) -amin'o-aryl of in claim 6, ,drying the fibers thusapplied to,

, steaming and finishing by rinsing and soaping.

the formula: 5

COTNHMZ.

(wherein Z means a'radical of the benzene "or" naphthalene series), which dyeing preparations azo-dyestuffs insoluble in waterand alkali.

8. As a new composition of matter the dyeing preparation consisting of 32, 0 parts of the sodium salt of 4-methoXy-diphenylamine-4-diazo-sulfonic acid 26, 3 parts of (2-hydroxy-naphthalene-Ii-carbonyl) -amino-benzene' 6 parts of finely ground sulfur 8 parts of powderous sodium hydroxide, which dyeing preparation yields, when brought onto fibers, by steaming clear navy blue dyeings and printings.

9. As a new composition of matter the dyeing preparation consisting of 10, 6 parts of the sodium salt of 3-methoxy-diphenylamine-4-diazo-sulfonic acid 10 parts of l-(2-hydroxy-naphthalene-3-carbonyl) -amino3nitro-benzene 3 parts of sodium hydroxide, which dyeing preparation yields, when brought onto fibers, by steaming greenish blue dyeings and printings.

10. As a new composition of matter the dyeing preparation consisting of p 30 parts of the disodium salt of diphenylamine- 4.4-bis-diazo-sulfonic acid 28, 6 parts of the disodium salt of l-(2-hydroxynaphthalene 3 carbonyl) -amino -3- nitrobenzene 8 parts of flowers of sulfur,

which dyeing preparation yields, when brought onto fibers, by steaming black dyeings and printings.

11. A process which comprises applying to vegetablei-fibers the dyeing preparations claimed in claim 1, drying the fibers thus applied to, steaming and finishing by rinsing and soaping.

12. A process which comprises applying to vegetable fibers the dyeing preparations claimed in claim 2, drying the fibers thus applied to, steaming and finishing by rinsing and soaping.

13. A process which comprises applying to vegetable fibers the dyeing preparations claimed in claim 3, drying the fibers thus applied to, steaming and finishing by rinsing and soaping. 5 14. A process which comprises applying to vegetable fibers the dyeing preparations claimed in claim 4, drying the fibers thus applied to, steaming and finishing by rinsingand soaping.

15. A process which comprises applying to vegetable fibers the dyeing preparations claimed in .claim 5, drying the fibers thus applied to, steaming and finishing by rinsing and soaping. 16. A process which comprises applying to vegetable fibers the dyeing preparations claimed 17. A process which comprises applying to vegetables fibers thedyeing preparations claimed inclaim 7 drying the fibers thus, applied to, steaming and finishing by rinsing and soaping.

18. A process which comprises printing vegetable. fibers with a paste containing 5 yield in the presence ,of caustic alkali by steaming t,

19. A process which comprises printing vegeno 20 parts of the sodium salt of 4-methoxy-diphenylamine-4-diazo-sulfonie acid 15 parts of (2 hydroxy naphthalene 3 car bonyl-amino) -benzene 20 parts of caustic, potash lye of 43 B.'

15 parts of alcohol 15 parts of thiodiglycol 15 parts of sodium chromate solution 1:4

50 parts of mucilage of tragacanth 65:1000

50 parts of water,

drying the fibers thus impregnated, steaming and finishing in the usual manner.

ARTHUR ZITSCHER. WILHELM SEIDENFADEN. KARL JELLINEK.

CERTIFICATE or- CORRECTION.

-Patent' Ti -1,920,542. Augustl, Tim

I ARTHUR zT T s'cnER, ET AL.

It is hereby certified that error appearsindthe printed specification of the above numbered patent requiring correction as follows: Page 2, line 51, for

"34"." read 43; page 3, column 1. line 72, for "4-amino-2.4-dimethoxy-" rend 4-amino-2.4-dimethoxy-; andline 144, column 5, for "Birght" read Bright; page 5, line l35, claims 20, for "in the usual manner" read by rinsing and soaping; and thatlthe said Letters Patent should be read with these corrections therein that the same may conform to the record of the case-in'the Patent Office.

.Siizned and sealed this 28th day of November, A 0.1933,

i M. Hopkins (Seal) v Acting Commissioner of Patents. 

